ω-Aliphatic and cycloaliphatic hydrocarbonoxy-2,6-alkadienoates and 2-alkenoates

ABSTRACT

The present invention concerns unsaturated ethers or thioethers of the formula: ##EQU1## wherein R 1  is an aliphatic or alicyclic hydrocarbon, R 2  and R 3  are H or alkyl, Y is cyano, amido, a ketone or an acid ester, ##EQU2## is an ether, thioether or a saturated or unsaturated c--c bond and n is an integer, which exhibit insecticidal properties.

This is a continuation of application Ser. No. 257,671 filed May 30,1972, now abandoned.

The present invention relates to unsaturated ethers or thioethers.

The present invention provides compounds of formula I, ##EQU3## whereinR₁ is alkyl of 1 to 10 carbon atoms; alkenyl of 3 to 10 carbon atoms;alkynyl of 3 to 10 carbon atoms; cycloalkyl of 3 to 6 carbon atoms;cycloalkyl of 3 to 6 carbon atoms substituted by alkyl of 1 to 4 carbonatoms; cycloalkenyl of 5 to 7 carbon atoms; cycloalkenyl of 5 to 7carbon atoms substituted by alkyl of 1 to 4 carbon atoms; cycloalkyl(of3 to 6 carbon atoms)alkyl (of 1 to 4 carbon atoms); cycloalkyl(of 3 to 6carbon atoms)alkyl (of 1 to 4 carbon atoms) ring substituted by alkyl of1 to 4 carbon atoms; cycloalkenyl(of 5 to 7 carbon atoms)alkyl (of 1 to4 carbon atoms); or cycloalkenyl(of 5 to 7 carbon atoms)alkyl (of 1 to 4carbon atoms) ring substituted by alkyl of 1 to 4 carbon atoms;

R₂ and R₃, which are the same or different, are each hydrogen or alkylof 1 to 4 carbon atoms,

Y is cyano;

    --CONR.sub.4 R.sub.5

wherein R₄ and R₅, which are the same or different, are each hydrogen oralkyl of 1 to 4 carbon atoms, or R₄ and R₅ together with the nitrogenatom constitute a 5 or 6 membered heterocycle containing either one ringnitrogen atom or one ring nitrogen atom and one ring oxygen atom, e.g.pyrrolidine, piperidine or morpholine;

    --COOR.sub.6

wherein R₆ is alkyl of 1 to 5 carbon atoms; or

    COR.sub.7

wherein R₇ is alkyl of 1 to 5 carbon atoms;

Q is oxygen or sulphur; ##EQU4## and n is an integer 1, 2 or 3.

When any of R₁, R₂, R₃, R₄, R₅, R₆ and R₇ are aliphatic groups of morethan 2 carbon atoms, they may be straight or branched chain.

The present invention also provides processes for the production of acompound of formula I which comprises

a. reacting a compound of formula II, ##EQU5## whereinR₁, R₂, R₃, Q,##EQU6## and n are as defined above with a compound of formula III,##EQU7## wherein Y is as defined above and R₈ and R₉, which are the sameor different, are each phenyl, alkoxy of 1 to 4 carbon atoms or aryloxy(e.g. phenyloxy or toluyloxy),

in the presence of a strong base (i.e. under Wittig-Horner conditions -Houben-Weyl, Methoden der Organischen Chemie, Ed. E. Muller, Vol.V/1cpage 603 [ 1970])

or

b. reacting a compound of formula II with a compound of formula IV,##EQU8## wherein Y is as defined above and R₁₀, R₁₁ and R₁₂ are eacharyl (e.g. phenyl, alkylphenyl, such as meta methyl-, ethyl-, n-propoyl-or i-propyl-substituted phenyl, alkoxyphenyl, such as para methoxy-,ethoxy-, n-propoxy- or i-propoxy- substituted phenyl, or chloro-orbromo-substituted phenyl, such as para chloro-substituted phenyl) ordialkylamino of 2 to 8 carbon atoms

or

c. reacting a compound of formula V, ##EQU9## wherein R₁, R₂, Q and nare as defined above, ##EQU10## and X is chlorine or bromine, with acompound of formula VI, ##EQU11## wherein R₃ and R₇ are as defined aboveand R₁₃ is alkyl of 1 to 4 carbon atoms,

with subsequent acid hydrolysis and dehydration, to produce a compoundof formula Ia, ##EQU12## wherein R₁, R₂, R₃, R₇, Q, ##EQU13## and n areas defined above or

d. reacting a compound of formula Ib ##EQU14## wherein R₁, R₂, R₃, R₆,Q, ##EQU15## and n are as defined above with a compound of formula VII,

    mnr.sub.4 r.sub.5                                          vii

wherein R₄ and R₅ are as defind above and

M is hydrogen, lithium or MgBr,

to produce a compound of formula Ic ##EQU16## wherein R₁, R₂, R₃, R₄,R₅, Q, ##EQU17## and n are as defined above.

Process (a) may, for example, be effected as follows, viz:

A strong base such as sodium hydride, in for example, an ether such as1,2-dimethoxyethane, tetrahydrofurane, diethylether or dioxane, or anamide such as dimethylformamide, as a solvent or as suspension medium,or potassium tert.butoxide in for example, benzene, toluene ortetrahydrofurane as a solvent or a suspension medium, or a sodiumalcoholate in for example dimethylformamide as a solvent or a suspensionmedium, may be added to a compound of formula VII, preferably whilestirring and conveniently at room temperature. The mixture may bestirred for a period of about 8 hours and a compound of formula II thenadded in a solvent, conveninetly that employed for the strong base. Themixture may be stirred for a period of about 20 hours conveniently atroom temperature after which time water may be added with cooling.Working up may be effected in conventional manner e.g. by extractionwith benzene.

Process (b) may, for example, be effected as follows viz:

A compound of formula II, in a solvent such as an ether, for example,dioxane or tetrahydrofurane, may be reacted with a compound of formulaIV, preferably at an elevated temperature, for example, at refluxtemperature, conveniently over a prolonged period, for example about 24hours. In some circumstances, the compound of formula IV mayconveniently be produced in situ. Working up may be effected inconventional manner.

Process (c) may, for example, be effected as follows viz:

A compound of formula VI may be added to a compound of formula V in asolvent such as an ether, for example diethyl ether or tetrahydrofurane.After a period of between about 2 and 6 hours, conveniently at roomtemperature, a dilute mineral acid such as dilute hydrochloric acid ordilute sulphuric acid may be added to the mixture, the resultingmagnesium salt and enol ether being hydrolysed with subsequentelimination of water. Working up may be effected in conventional manner.

Process (d) may, for example, be effected as follows viz:

A compound of formula VII in a solvent such as absolute ether may beadded to a compound of formula Ib in the same solvent conveniently withstirring and at room temperature. The reaction may be allowed to proceedover a prolonged period e.g. up to 12 hours. Working up is effected inmanner known per se.

The compound of formula II employed as starting material in processes(a) and (b) above may be produced as follows viz:

a'. The compounds of formula IIa, ##EQU18## wherein R₁, R₂, R₃, Q and nare as defined above may be produced by reacting a compound of formulaVIII, ##EQU19## wherein R₁, R₂, Q and n are as defined above with acompound of formula XIII, ##EQU20## wherein R₃ is as defined above andR₁₄ is methyl or ethyl,

in manner known per se.

b'. The compounds of formula IIb ##EQU21## wherein R₁, R₂, R₃, Q and nare as defined above and ##EQU22## may be produced by etherifying acompound of formula IX, ##EQU23## wherein R₁, R₂, Q, ##EQU24## and n areas defined above, with a compound of formula X, ##EQU25## wherein R₃ isas defined above, in manner known per se.

c'. The compounds of formula IIc, ##EQU26## wherein R₁, R₂, R₃, Q,##EQU27## and n are as defined above, may be produced by reacting acompound of formula XI, ##EQU28## wherein R₁, R₂, Q, ##EQU29## n and Xare as defined above, with a compound of formula XIII with subsequenthydrolysis and decarboxylation, in manner known per se.

d'. The compounds of formula IId, ##EQU30## wherein R₁, R₂, Q and n areas defined above, may be produced by reacting a compound of formulaVIII, with an alkylvinyl ether of 3 to 7 carbon atoms, in the presenceof mercuric acetate. The reaction may be effected at elevatedtemperature and over a prolonged period e.g. 4 days, with subsequentrearrangement while heating at a temperature of, for example,160°-190°C, over a period of, for example, 1 to 2 hours.

e'. The compounds of formula IIe ##EQU31## wherein R.sub. 1 ' is alkylof 1 to 10 carbon atoms; cycloalkyl of 3 to 6 carbon atoms; cycloalkylof 3 to 6 carbon atoms substituted by alkyl of 1 to 4 carbon atoms;cycloalkyl (of 3 to 6 carbon atoms)alkylene(of 1 to 4 carbon atoms); orcycloalkyl(of 3 to 6 carbon atoms)alkylene(of 1 to 4 carbon atoms) ringsubstituted by alkyl of 1 to 4 carbon atoms; and

R₂, r₃, q and n are as defined above,

may be produced by catalytic hydrogenation of a compound of formula IIf##EQU32## wherein R₁ ', R₂, R₃, Q and n are as defined above, inconventional manner.

The compounds of formula VIII may, for example, be produced by reactinga compound of formula XII, ##EQU33## wherein R₁, R₂, Q and n are asdefined above, with vinyl magnesium chloride or bromide.

The compounds of formulae III, IV, V, VI, VII, IX, X, XI, XII and XIIIare either known or may be produced in analogous manner to the processfor producing the known compounds.

The compounds of formula I are colourless oils. They may becharacterised and purified in the normal manner e.g. purification bydistillation or chromatography.

The compounds of formula I are useful as insecticides as indicated inthe following tests by an inhibiting effect on the development of theinsects Dysdercus Fasciatus (Egyptian cotton worm) and Prodenia littura(cotton stainer) from one development stage thereof to the next, toresult either the death, reduced oviposition or inhibition ofcopulation.

Test 1: Insecticidal effect on Dysdercus fasciatus larvae (Egyptiancotton worm)

Filter paper is impregnated with a solution of a compound of formula Iviz:

a. methyl-[9-sec.butoxy-3,7-dimethyl]2,6-nonadienoate,

b. 9-sec.butoxy-3,7-dimethyl-2,6-nonadiene-1-nitrile, and

c. methyl-[9-isopropoxy-3,7-dimethyl]2,6-nonadienoate, at aconcentration of 0.1 mg/cm².

A box made from polystyrene (200 × 100 × 85 mm) is coated with thefilter paper treated in this way. A folded filter paper, which is alsoimpregnated, is covered with about 30 Dysdercus larvae of the 4th larvalstage and placed into the box. Pounded cotton seeds as food and adrinking-vessel are placed into it. The mortality is determined after 10days. Substantial mortality is observed.

Test 2: Effect on the development of Prodenia-littura larvae (cottonstrainer) into adults

Filter paper is impregnated with a solution of a compound of formula Iviz:

a. methyl-[9-sec.butoxy-3,7-dimethyl]2,6-dienoate and

b. methyl-[9-isopropoxy-3,7-dimethyl]2,6-nonadienoate, at aconcentration of 0.1 mg/cm² Partitions, having a size of 3.5 × 5.5 cm,of a plastic box are coated with the filter paper treated in this way.One Prodenia caterpillar in the third to fourth larval stage is placedinto each partition and a piece of artificial medium is given as food.The insects are kept at 25°. The number of the adults which havedeveloped normally after 21 days is determined. The rate of developmentis found to be substantially checked.

In addition, the compounds of formula I are further useful asinsecticides because they exhibit low toxicity towards warm bloodedanimals.

It is to be understood that the term "insects" as used herein is used ina broad sense and may include not only the class Insecta, but classes ofsimilar or related organisms e.g. spider mites. The term "insecticide"and "insecticidal" as used herein should be construed accordingly.

For the abovementioned use, the amount applied to a locus to be treatedwill of course vary depending on the compound employed, the mode ofapplication, ambient conditions, and the insects to be combated.However, with regard to plant protection, satisfactory results areobtained when applied to a plant locus in an amount of between 1 and 4kg/hectare, the application being repeated as required.

The compounds may be applied to the locus with conventional applicatorequipment and by conventional methods e.g. strewing, spraying anddusting.

Compositions may comprise a compound of formula I in admixture withinsecticidal carriers, insecticidal diluents and/or insecticidaladjuvants in solid or liquid form e.g. spraying and dusting powders,granulates, liquid sprays and aerosols.

Solid forms may include diluents and carriers such as diatomaceousearth, bentonite and pumice. Adjuvants e.g. surfactants such as wettingand dispersing agents and adhesive agents, e.g. cellulose derivatives,may also be included in the case of wettable powders to be applied as awater suspension. Granulates are produced by coating or impregnatinggranular carrier materials such as pumice, limestone, attapulgite andkoalinite with the compounds.

Liquid forms may include non-phytotoxic diluents and carriers such asalcohols, gylcolic ethers, aliphatic and aromatic hydrocarbons e.g.xylene, alkyl napthalenes and other petroleum distillates. Adjuvantssuch as surface active agents, e.g. wetting and emulsifying agents suchas polyglycol ethers formed by the reaction of an alkylene oxide withhigh molecular weight alcohols, mercaptans or alkyl phenols, may beincluded in emulsion concentrate forms. Appropriate organic solventse.g. ketones, aromatic optionally halogenated hydrocarbons and mineraloils may also be included as solvent aids.

Aside from the abovementioned carriers, diluents and adjuvants,adjuvants such as U.V. stabilizing agents, desactivators (for solidforms with carriers having an active surface), agents for improvingadhesiveness to surfaces treated, anticorrosives, defoaming agents andpigments may also be included.

Concentrate forms of composition generally contain between 2 and 90%,preferably between 5 and 50 %, by weight of active compound.

Application forms of composition generally contain at least 0.01 % andpreferably between 0.1 and 20 % by weight of active compound.

Examples of concentrate forms of composition will now be described.

a. Emulsifiable concentrate

25 parts by weight of a compound of formula I are mixed with 25 parts byweight of isooctylphenyldecaglycol ether and 50 parts by weight ofxylene, whereby a clear solution is obtained which may be readilyemulsified in water. The concentrate may be diluted with water to thedesired concentration.

b. Emulsifiable concentrate

25 parts by weight of a compound of formula I are mixed with 30 parts byweight of isooctylphenyloctaglycol ether and 45 parts by weight of apetroleum fraction having a B.P. of 210°-280° (D₂₀ : 0.92). Theconcentrate may be diluted with water to the desired concentration.

c. Emulsfiable concentrate

50 parts by weight of a compound of formula I are mixed with 50 parts byweight of isooctylphenyloctaglycol ether. A clear concentrate isobtained which may be readily emulsified in water and which may bediluted with water to the desired concentration.

The preferred compounds of formula I are generally those compoundwherein

R₁ is alkyl of 1 to 6 carbon atoms,

R₂ and R₃, which are the same or different, are each hydrogen or alkylof 1 to 4 carbon atoms,

Q is oxygen, ##EQU34## Y is cyano; COOR₆ wherein R₆ is alkyl of 1 to 5carbon atoms; or COR₇ wherein R₇ is alkyl of 1 to 5 carbon atoms and

n is an integer 1, 2 or 3.

Specific preferred compounds are

methyl-[9-sec.butoxy-3,7-dimethyl]2,6-nonadienoate,

9-sec.butoxy-3,7-dimethyl-2,6-nonadiene-1-nitrile

and methyl-[9-isopropoxy-3,7-dimethyl]2,6-nonadienoate.

The following Examples illustrate the production of the compounds offormula I, but in no way limit the invention. The temperatures areindicated in degrees Centigrade. Where concentration is indicated as apercent, this is percent by weight. Where pressure is indicated in mmthis is mm/Hg.

EXAMPLE 1: Methyl-[9-sec.butoxy-3,7-dimethyl]-2,6-nonadienoate [processa)]

1.31 g (0.03 mol) of a 55 % sodium hydride emulsion in mineral oil arewashed with hexane and suspended in 45 cc of 1,2-dimethoxy ethane in anatmosphere of nitrogen. 6.3 g (0.03 mol) ofmethyl-(0,0-diethyl-phosphono)acetic acid are added at 20°-25° duringthe course of 1 hour and while stirring. After 8 hours 4.24 g (0.02 mol)of 8-sec.butoxy-6-methyl-5-octen-2-one in 6 cc of 1,2-dimethoxy ethaneare added dropwise and the mixture is stirred at 20°-25° for 20 hours.Working up is effected by the dropwise addition of 100 c of water withcooling. The organic phase is extracted with benzene; the benzeneextract is concentrated by evaporation to 60 cc, is filtered through 30g of aluminium oxide (activity II) and the filtrate is evaporated. Theresidue may be purified on silica gel by chromatography [eluanthexane/acetic ester (9:1)], whereby a cis/trans isomeric mixture ofmethyl-[9-sec.-butoxy-3,7-dimethyl]-2,6-nonadienoate is obtained.

n_(D) ²⁰ = 1.4678

Analysis: C₁₆ H₂₈ O₃ - Molecular weight 268.4: Calc. C 71.6 %; H 10.5 %;O 17.9 %; Found C 71.9 %; H 10.2 %; O 18.3 %

EXAMPLE 2: Methyl-[9-isopropoxy-3,7-dimethyl]-2,6-nonadienoate [processa)]

The above compound is produced in analogous manner to that described inExample 1, but using 8-isopropoxy-6-methyl-5-octen-2-one in place of8-sec.-butoxy-6-methyl-5-octen-2-one.

n_(D) ²⁰ = 1.4691

Analysis: C₁₅ H₂₆ O₃ - Molecular weight: 254.4: Calc. C 70.8 %; H 10.3%; Found C 71.2 %; H 10.4 %

EXAMPLE 3: Methyl-[5-(4-isopropoxy-2-butyloxy)-3-methyl]-2-pentenoate[process a)]

The above compound is produced in analogous manner to that described inExample 1, but using 4-(4-isopropoxy-2-butyloxy)-2-butanone in place of8-sec.-butoxy-6-methyl-5-octen-2-one.

n_(D) ²⁰ = 1.4521

Analysis: C₁₄ H₂₆ O₄ - Molecular weight: 258.4: Calc. C 65.1 %; H 10.1%; Found C 65.4 %; H 10.4 %

EXAMPLE 4: Ethyl-[10-isopropoxy-3-methyl]-2-decenoate [process a)]

The above compound is produced in analogous manner to that described inExample 1, but using 9-isopropoxy-2-nonanone in place of8-sec.butoxy-6-methyl-5-octen-2-one andethyl-(0,0-diethyl-phosphono)-acetic acid in place ofmethyl-(0,0-diethyl-phosphono)-acetic acid.

n_(D) ²⁰ = 1.4527

Analysis: C₁₆ H₃₀ O₃ - Molecular weight: 270.4: Calc. C 71.1 %; H 11.2%; O 17.7 %; Found C 71.6 %; H 11.2 %; O 17.7 %

EXAMPLE 5: Methyl-[5-(1-sec.butoxy-3-pentyloxy)-3-methyl]-2-pentenoate[process a)]

The above compound is synthesized in analogous manner to that describedin Example 1. The 4-(1-sec-butoxy-3-pentyloxy)-2-butanone used asstarting material in place of 8-sec.butoxy-6-methyl-5-octen-2-one isproduced in accordance with Example 14 below.

n_(D) ²⁰ = 1.4527

Analysis: C₁₆ H₃₀ O₄ - Molecular weight: 286.4: Calc. C 67.1 %; H 10.6%; Found C 68.0 %; H 10.7 %

EXAMPLE 6: Ethyl-[9-isopropoxy-3,7-dimethyl]-2-nonenoate [process a)]

The above compound is produced in analogous manner to that described inExample 1, but using ethyl-(0,0-diethylphosphono)-acetic acid in placeof methyl-(0,0-diethylphosphono)-acetic acid and8-isopropoxy-6-methyl-2-octanone in place of8-sec.butoxy-6-methyl-5-octen-2-one.

n_(D) ²⁰ = 1.4532

Analysis: C₁₆ H₃₀ O₃ - Molecular weight: 270.4: Calc. C 71.1 %; H 11.2%; O 17.7 %; Found C 70.7 %; H 10.8 %; O 18.4 %

EXAMPLE 7: 10-Isopropoxy-8-methyl-3,7-decadien-2-one [process b)]

1.84 g (0.01 mol) of 7-isopropoxy-5-methyl-4-heptenal and 3.18 g (0.01mol) of triphenyl-acetyl methylene phosphorane (M.P. 199.5°-201.5°),produced in accordance with D. B. Denney and S. T. Ross, J. Org. Chem.27, 998 [1962], are boiled together under reflux for 24 hours in 30 ccof tetrahydrofurane. The tetrahydrofurane is then evaporated, theresidue is taken up in hexane, and filtered off from the insoluble partand the hexane is evaporated. The oily residue may be purified bychromatography on silica gel with benzene/methanol 96:4. Pure10-isopropoxy-8-methyl-3,7-decadien-2-one is obtained.

n_(D) ²⁰ = 1.4716

Analysis: C₁₄ H₂₄ O₂ - Molecular weight: 224.3: Calc. C 75.0 %; H 10.8%; Found C 75.1 %; H 10.9 %

EXAMPLE 8: 9-sec.Butoxy-3,7-dimethyl-2,6-nonadiene-1-nitrile [processa)]

To a suspension of 0.48 g (0.01 mol) of 50 % sodium hydride dispersionin 25 cc of absolute 1,2-dimethoxy ethane there is added dropwise at 25°1.77 g (0.01 mol) of 0,0-diethylcyano methyl phosphonate. After stirringfor 2 hours at 25°, 2.12 g (0.01 mol) of8-sec.butoxy-6-methyl-5-octen-2-one are added and the mixture is stirredover the course of 18 hours at 25°. 50 cc of ether and 150 cc of waterare subsequently added and the aqueous phase is extracted with ether.The ether extract is washed with saturated salt solution, dried withsodium sulphate and evaporated. The residue is chromatographed on silicagel with chloroform as eluant, whereby the9-sec.butoxy-3,7-dimethyl-2,6-nonadiene-1-nitrile is obtained ascolourless oil consisting of about equal parts of the cis and transisomers.

n_(D) ²⁰ = 1.4720

Analysis: C₁₅ H₂₅ NO - Molecular weight: 235.4: Calc. C 76.5 %; H 10.7%; N 6.0 %; Found C 77.0 %; H 10.9 %; N 5.6 %

EXAMPLE 9: 10-Isopropoxy-4,8-dimethyl-3,7-decadien-2-one [process c)]

To the Grignard reagent, produced from 0.46 g (0.019 mol) of magnesiumand 4.5 g (0.019 mol) of 1-bromo-6-isopropoxy-4-methyl-3-hexene in 60 ccof absolute ether, there is added dropwise at 5° over the course of 15minutes and while stirring, a solution of 2.45 g (0.019 mol) of4-ethoxy-3-penten-2-one. After stirring for 4 hours at 20° the mixtureis poured on ice cold 2N sulphuric acid and is extracted with ether. Theether extract is washed with saturated sodium bicarbonate solution,water and saturated salt solution, then dried over sodium sulphate andevaporated. After chromatography of the residue on 200 g of silica gelwith hexane/ethyl acetate (9:1) as eluant,10-isopropoxy-4,8-dimethyl-3,7-decadien-2-one is obtained as acolourless oil.

n_(D) ²⁰ = 1.4726

Analysis: C₁₅ H₂₆ O₂ - Molecular weight: 238.4: Calc. C 75.5%; H 10.9 %;Found C 74.6 %; H 10.9 %

EXAMPLE 10: N,N-diethyl-[9-isopropoxy-3,7-dimethyl]-2-nonenoic acidamide [process d)]

1.46 g (0.02 mol) of diethylamine in 10 ml of absolute ether are addedto a 6 ml of a 20 % solution of butyllithium in hexane in a nitrogenatmosphere with stirring at -10°. The reaction mixture is then stirredfor 1 hour at 20° when it is added to a solution of 5.4 g (0.02 mol) ofethyl-[9-isopropoxy-3,7-dimethyl]-2-nonenoate (produced in accordancewith Example 6) in 10 ml of absolute ether.

After 4 hours at 25°, 10 ml of water, followed by 10 ml of 0.2 % sodiumchloride solution, are added to the reaction mixture. The aqueous phaseis extracted with ether, the ether extract is washed with water, driedwith sodium sulphate and the ether evaporated off.

After chromatography on a silica gel column with hexane/acetic acidester (9:1) as eluant, N,N-diethyl-[9-isopropoxy-3,7-dimetyl]-2-nonenoicacid amide, -dimethyl]a colourless oil is obtained.

Analysis: C₁₈ H₃₅ NO₂ - Molecular weight: 297.4: Calc. C 72.7 %; H 11.8%; N 4.7 %; Found C 72.1 %; H 11.5 %; N 4.4 %

The following compounds of formula I may be produced by an analogousprocess to that described in the preceding Examples. The significancesfor R₁, R₂, R₃, Q, ##EQU35## Y and n, and the preceding Exampleaccording to which the compounds may be produced are set out set below:

                               |                                         R.sub.1        R.sub.2                                                                            R.sub.3                                                                            Q --Z.sub.1 --Z.sub.2 --                                                                Y   n Example                              __________________________________________________________________________                               |                                         n-decyl       n-butyl                                                                            methyl                                                                              S --CH--S--                                                                           n-pentoxy-                                                                          1 1                                                                     carbonyl                                                                |                                         ethyl         methyl                                                                             sec.butyl                                                                           0 --C=CH--                                                                            n-pentyl-                                                                           1 9                                                                     carbonyl                                                                |                                         9-decenyl     methyl                                                                             methyl                                                                              0 --C=CH--                                                                            aminocar-                                                                           1 1                                                                     bonyl                                                                   |                                         propargyl     methyl                                                                             methyl                                                                              0 --CH--O--                                                                           di-n-but-                                                                           1 1                                                                     ylamino-                                                                      carbonyl                                                                |                                         9-decinyl     methyl                                                                             methyl                                                                              S --CH--S--                                                                           pyrroli-                                                                            1 1                                                                     dinocar-                                                                      bonyl                                                                   |                                         cyclopropanyl methyl                                                                             methyl                                                                              S --CH--S--                                                                           piperidi-                                                                           1 1                                                                     nocarbonyl                                                              |                                         2-methylcyclopropanyl                                                                       methyl                                                                             methyl                                                                              S --CH--S--                                                                           morpholi-                                                                           1 1                                                                     nocarbonyl                                                              |                                         2-tert.butylcyclopro-                                                                       methyl                                                                             methyl                                                                              0 --CH--O--                                                                           pyrrolidi-                                                                          2 1                                    panyl                            nocarbonyl                                                               |                                        4(2-tert.butylcyclopro-                                                                     methyl                                                                             methyl                                                                              0 --CH--O--                                                                           pyrrolidi-                                                                          2 1                                    panyl)-n-butyl                   nocarbonyl                                                              |                                         cyclopentenyl methyl                                                                             methyl                                                                              0 --CH--O--                                                                           piperidi-                                                                           2 1                                                                     nocarbonyl                                                              |                                         cyclohexyl    methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                                                     carbonyl                                                                |                                         4-methylcyclohexyl                                                                          methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                                                     carbonyl                                                                |                                         4-n-butylcyclohexyl                                                                         methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                                                     carbonyl                                                                |                                         4(4-n-butylcyclohexyl)-                                                                     methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                    n-butyl                          carbonyl                                                                |                                         2-cyclohexenyl                                                                              methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                                                     carbonyl                                                                |                                         4-methyl-3-cyclo-                                                                           methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                    hexenyl                          carbonyl                                                                |                                         4-n-butyl-3-cyclo-                                                                          methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                    hexenyl                          carbonyl                                                                |                                         4-(4-n-butyl-3-cyclo-                                                                       methyl                                                                             methyl                                                                              0 --C=C--                                                                             methoxy-                                                                            2 1                                    hexenyl-n-butyl                  carbonyl                                     __________________________________________________________________________

STARTING MATERIALS

Compounds of formula II: The following Examples 11 to 20 arerepresentative of the processes for the production of the compounds offormula II employed as starting material in processes (a) and (b).

EXAMPLE 11: 8-sec.Butoxy-6-methyl-5-octon-2-one

8.06 g (0.05 mol) of 5-sec.butoxy-3-methyl-1-penten-3-ol and 11.6 g (0.1mol) of acetoacetic acid methyl ester are heated to 135° in a roundbottom flask with a fractionating column and in an atmosphere ofnitrogen. The methyl alcohol which is liberated during the reactiondistils into the receiver. After 1 hour the reaction temperature isincreased to 182°-185° at which temperature the reaction mixture ismaintained for 5 hours. After cooling, the reaction mixture isfractionally distilled at reduced pressure. A cis/trans mixture of8-sec.butoxy-6-methyl-5-octen-2-one is obtained. B.P. 105°-109°/0.8 mm.

n_(D) ²⁰ = 1.4534

Analysis: C₁₃ H₂₄ O₂ - Molecular weight: 212.3: Calc. C 73.5 %; H 11.4%; Found C 73.4 %; H 10.9 %

EXAMPLE 12: 8-Isopropoxy-6-methyl-5-octen-2-one

The compound is produced in analogous manner to that described inExample 11, but using 5-isopropoxy-3-methyl-1-penten-3-ol in place of5-sec.butoxy-3-methyl-1-penten-3-ol. B.P. 117°-119°/8 mm.

n_(D) ²⁰ = 1.4473

Analysis: C₁₂ H₂₂ O₂ - Molecular weight: 198.3: Calc. C 72.7 %; H 11.2%; Found C 72.4 %; H 11.0 %

EXAMPLE 13: 8-Isopropylthio-6-methyl-5-octen-2-one

The above compound is produced in analogous manner to that described inExample 11, except that 5-isopropylthio-3-methyl-1-penten-3-ol is usedin place of 5-sec.butoxy-3-methyl-1-penten-3-ol and that the reactionmixture is purified not by distillation but by chromatography on silicagel with hexane/ethyl acetate (9:1) as eluant.

n_(D) ²⁰ = 1.4883

Analysis: C₁₂ H₂₂ OS - Molecular weight: 214.4: Calc. C 67.3 %; H 10.2%; S 15.0 %; Found C 66.4 %; H 9.7 %; S 15.0 %

EXAMPLE 14: 4-(4-Isopropoxy-2-butyloxy)-2-butanone

10 g (0.26 mol) of sodium borohydride are added at 20°-25°, over thecourse of 2 hours to 20 g (0.154 mol) of 4-isopropoxy-2-butanone,dissolved in 200 cc of ethanol. After a further 2 hours, the reactionmixture is concentrated by evaporation to 50 cc at reduced pressure,poured into 400 cc of water and the product extracted with ether. Theether solution is dried with sodium sulphate and evaporated. The residueis distilled at 35 mm, whereby 4-isopropoxy-2-butanol, having a B.P. of88°/35 mm is obtained.

A mixture of 9.9 g (0.075 mol) of 4-isopropoxy-2-butanol and 7.0 g (0.1mol) of methylvinyl is added dropwise at 20°-30° over the course of 30minutes, to 3.3 g (0.025 mol) of 4-isopropoxy-2-butanol and 0.4 g ofconcentrated sulphuric acid. After stirring for 24 hours at 20°-25°, 0.7g of potassium carbonate and 0.1 g of water are added. The reactionmixture is vigorously stirred at room temperature over the course of 3hours, filtered and distilled. The resulting4-(4-isopropoxy-2-butyloxy)-2-butanone has a B.P. of 75°-76°/1.0 mm.

n_(D) ²⁰ = 1.4268

Analysis: C₁₁ H₂₂ O₃ - Molecular weight: 202.3: Calc. C 65.3 %; H 11.0%; Found C 65.0 %; H 11.0 %

EXAMPLE 15: 4-(1-sec.Butoxy-3-pentyloxy)-2-butanone

The above compound is produced in analogous manner to that described inExample 14, but using 1-isopropoxy-3-pentanone in place of4-isopropoxy-2-butanone. B.P. 95°-97°/1.2 mm.

n_(D) ²⁰ = 1.4306

Analysis: C₁₃ H₂₆ O₃ - Molecular weight: 230.3: Calc. C 67.8 %; H 11.4%; Found C 67.8 %; H 11.2 %

EXAMPLE 16: 7-Isopropoxy-5-methyl-4-heptenal

15.8 g (0.1 mol) of 5-isopropoxy-3-methyl-1-penten-3-ol and 20.0 g ofmercuric acetate in 180 cc of ethyl vinyl ether are maintained at refluxtemperature over the course of 4 days. 0.9 cc of glacial acetic acid isadded at 20° to the turbid solution. After 3 hours 150 cc of 5 %potassium carbonate solution are added and the product is extracted withhexane. The hexane extract is dried with sodium sulphate and evaporated.The residue is heated to 165°-168° over the course of 11/2 hours withoutfurther purification and in an atmosphere of nitrogen; the residue issubsequently distilled at reduced pressure. The7-isopropoxy-5-methyl-4-heptenal has a B.P. of 70°-73°/0.8 mm.

n_(D) ²⁰ = 1.4476

Analysis: C₁₁ H₂₀ O₂ - Molecular weight: 184.3: Calc. C 71.7 %; H 10.9%; Found C 71.7 %; H 10.8 %

EXAMPLE 17: 9-Isopropoxy-2-nonanone

1.4 g (0.025 mol) of solid potassium hydroxide are dissolved in 30 cc of50 % aqueous methanol. 4.1 g (0.015 mol) of3-carbethoxy-9-isopropoxy-2-nonanone are added to this solution and themixture is heated to boiling temperature. After 1 hour at reflux thereaction mixture is cooled to 50°, neutralized with 50 % sulphuric acid,cooled to room temperature after 10 minutes, and 50 cc of water added.The product is extracted from the heterogeneous mixture with ether, theether extract is washed with saturated salt solution, dried with sodiumsulphate and evaporated. The residue is chromatographed on silica gelwith hexane/ethyl acetate 9:1. Pure 9-isopropoxy-2-nonanone is obtainedas a colourless oil.

n_(D) ²⁰ = 1.4309

Analysis: C₁₂ H₂₄ O₂ Molecular weight: 200.3: Calc. C 72.0 %; H 12.1 %;O 16.0 %; Found C 71.7 %; H 11.9 % O 16.2 %

EXAMPLE 18: 8-Isopropoxy-6-methyl-2-octanone

The compound is produced in analogous manner to that described inExample 17, but using 3-carbethoxy-8-isopropoxy-6-methyl-2-octanone inplace of

3-carbethoxy-9-isopropoxy-2-nonanone. B.P. 127°-129°/15 mm.

Analysis: C₁₂ H₂₄ O₂ - Molecular weight: 200.3: Calc. C 72.1 %; H 12.1%; O 16.0 %; Found C 71.3 %; H 11.8 % O 17.3 %

EXAMPLE 19: 3-Carbethoxy-9-isopropoxy-2-nonanone

0.69 g (0.03 mol) of sodium are added at 20° to 20 cc of absoluteethanol. After complete reaction, 3.9 g (0.03 mol) of acetoacetic esterare added dropwise at 25° to the solution. The clear solution is thenheated to 80° and over a period of 1 hour, 6.7 g (0.03 mol) of1-bromo-6-isopropoxy-hexane are added dropwise at reflux temperature.The turbid mixture is boiled at reflux for 16 hours and subsequentlycooled to 20° and neutralized with alcoholic hydrochloric acid. Afteradding 20 cc of ether, the reaction mixture is filtered and the filtrateis evaporated. The residue is distilled, whereby, according togas-chromatography, pure 3-carbethoxy-9-isopropoxy-2-nonanone, having aB.P. of 125°-130°/0.8 mm, is obtained.

Analysis: C₁₅ H₂₈ O₄ - Molecular weight: 272.4; Calc. C 66.1 %; H 10.4%; O 23.5 %; Found C 65.8 %; H 10.4 %; 24.1 %

EXAMPLE 20: 3-Carbethoxy-8-isopropoxy-6-methyl-2-octanone

In manner analogous to that described in Example 19, the title compoundmay be produced, using 1-bromo-5-isopropoxy-3-methyl-pentane in place of1-bromo-6-isopropoxy-hexane. B.P. 92°-94°/10.sup.⁻⁴ mm.

Analysis: C₁₅ H₂₈ O₄ -Molecular weight: 272.4; Calc. C 66.1 %; H 10.4 %;O 23.5 %; Found C 66.1 %; H 10.0 %; O 23.9 %

Compounds of formula XI:

The following Examples 21 and 22 are representative of the process forproducing compounds of formula XI.

EXAMPLE 21: 1-Bromo-6-isopropoxy-hexane

1.15 g (0.05 mol) of finely cut sodium are added to 30 g (0.5 mol) ofabsolute isopropanol in an atmosphere of nitrogen; the mixture isstirred at 60° for 16 hours in order to dissolve the sodium completely.After cooling to 20°, 12.2 g (0.05 mol) of 1,6-dibromohexane are addedand the mixture is stirred at reflux temperature for 18 hours. Theprecipitated sodium bromide is filtered off, the excess isopropanol isremoved and the filtrate is distilled under vacuum. The main fraction(6.0 g), having a B.P. of 96°-98°/15 mm, is chromatographed on 300 g ofsilica gel with hexane/ethyl acetate (99:1), whereby1-bromo-6-isopropoxy-hexane is obtained as a colourless oil.

Analysis: C₉ H₁₉ BrO - Molecular weight: 223.2; Calc. C 48.4 %; H 8.5 %;Br 35.8 %; O 1.2 %; Found C 48.7 %; H 8.4 %; Br 35.9 %; O 7.6 %

EXAMPLE 22: 1-Bromo-5-isopropoxy-3-methyl-pentane

A mixture of 16 g (0.1 mol) of 5-isopropoxy-3-methyl-1-pentanol and 2 g(/.25 mol) of pyridine is added dropwise at 0° to 10.9 g (0.04 mol) ofphosphorous tribromide. The mixture is subsequently stirred at 25° for 2hours and is then distilld at a bath temperature of 160°/12 mm into areceiver containing saturated sodium bicarbonate solution. (B.P.100°-110°/12 mm).

The contents of the receiver are taken up with ether and successivelywashed with saturated sodium bicarbonate solution, 2N sulphuric acid,and saturated salt solution and dried with sodium sulphate. The ether isevaporated and the remaining 1-bromo-5-isopropoxy-3-methyl-pentane ispurified by distillation. B.P. 90°-91°/12 mm.

Analysis: C₉ H₁₉ Bro - Molecular weight: 223.2: Calc. C 48.4 %; H 8.6 %;Br 35.8 %; O 7.2%; Found C 48.4 %; H 7.9 %; Br 35.6 %; 7.7 %

The alcohols, used for the production of the compounds of formula XI,may be produced in accordance with known processes, e.g. as described inthe following Example

EXAMPLE 23: 5-Isopropoxy-3-methyl-pentanol

A mixture of 34.4 g (0.261 mol) of 4-isopropoxy-2-butanol and 5.07 g(0.064 mol) of absolute pyridine is added dropwise at 0°C over thecourse of 15 minutes and while stirring to 28.4 g (0.105 mol) ofphosphorous tribromide. After stirring for 2 hours at room temperaturethe reaction mixture is rapidly distilled in a vacuum B.P. 35°-60°/12mm. The distillate is taken up in ether, successively washed with icecold dilute sodium bicarbonate solution water, ice cold 2N sulphuricacid, water and then saturated sodium chloride solution, dried oversodium sulphate and separated from the ether by fractional distillation.

The residue is fractionally distilled and 2-bromo-4-isopropoxy-butane,having a B.P. of 69°-70°/24 mm, is obtained.

To an ethanolic sodium ethanolate solution, produced from 9.45 g ofsodium and 200 cc of absolute ethanol, is added, in an atmosphere ofnitrogen at 50°C over a period of 15 minutes while stirring, 67.7 g(0.423 mol) of diethyl-malonate, and subsequently 80.0 g (0.410 mol) of2-bromo-4-isopropoxy-butane over a further period of 15 minutes. Themixture is boiled at reflux for 24 hours, then neutraliued with glacialacetic acid and separated from the main amount of ethanol bydistillation.

The residue is treated with ice-water, and extracted with ether. Theether extract is washed with water and saturated salt solution, driedover sodium sulphate and the ether evaporated off in a vacuum. Theresulting crude ethyl-[2-carbethoxy-5-isopropoxy-3-methyl]-n-pentanoatemay be reacted without additonal purification.

110 g of crude ester are added dropwise at 60° over a period of 15minutes and while stirring to 180 g of 50 % KOH (1.60 mol) and themixture is boiled at reflux for 2 hours. After adding 100 cc of waterthe ethanol produced by hydrolysis is distilled off at normal pressure.The residue, acidified with 250 cc of 6N sulphuric acid at 10°C whilestirring is extracted with ether, the ether extract is washed with asmall amount of water and saturated sodium chloride, dried over sodiumsulphate and evaporated. The remaining crude dicarbonic acid isdecarboxylated by stirring at 190°C for 1 hour and the product issubsequently distilled in a vacuum. 5-Isopropoxy-3-methyl-n-pentanoicacid, having a B.P. of 89°-91°C/0.1 mm, is obtained.

Analysis: C₉ H₁₈ O₃ - Molecular weight: 174.2: Calc. C 62.0 %; H 10.4 %;O 27.5 %; Found C 62.0 %; H 10.4 %; O 27.6 %

A solution of 19.8 g (0.114 mol) of 5-isopropoxy-3-methyl-n-pentanoicacid in 120 cc of absolute benzene is added dropwise over a period of 1hour to 96 cc (0.342 mol) of 70 %sodium-bis-(2-methoxy-ethoxy)-aluminium-dihydride in 220 cc of absolutebenzene. The mixture is boiled at reflux for 2 hours, cooled to 10°C,acidified with 2N sulphuric acid while stirring and is extracted withether. The ether extract is washed with a small amount of water andsaturated sodium chloride solution, dried over sodium sulphate and theether evaporated off.

The residue is chromatographed with hexane: ethyl acetate 9:1) on 600 gof silica gel and 5-isopropoxy-3-methyl-pentanol is obtained ascolourless oil.

Analysis: C₉ H₂₀ O₂ - Molecular weight: 160.3: Calc. C 67.5 %; H 12.6 %;O 20.0 %; Found C 67.3 %; H 12.7 %; O 20.2 %

The halide stage which is employed in the production of the Grignardcompounds of formula V, employed in the production of compounds offormula I in accordance with process c), may, for example, be producedin accordance with the following Example.

EXAMPLE 24: 1-Bromo-6-isopropoxy-4-methl-3-hexane

To the Grignard reagent [production according to E. Renk et al. J. Am.Chem. Soc. 83, 1987 (1961)], from 9.06 g (0.37 mol) of magnesium and42.8 g (0.35 mol) of cyclopropyl bromide in 460 cc of absolutetetrahydrofurane, is added dropwise at 5°C over the course of 10minutes, in an atmosphere of nitrogen and while stirring, a solution of46 g (0.35 mol) of 4-isopropoxy-2-butanone in 100 cc of absolutetetrahydrofurane. After stirring the reaction mixture at roomtemperature for 20 hours, saturated ammonium chloride solution and iceare added and the mixture is extracted with ether. The ether extract iswashed with saturated salt solution, dried over sodium sulphate and theether evaporated off. The resulting 2-cyclopropyl-4-isopropoxy-2-butanolis obtained after distillation at 75°-79°/12 mm as a colourless oil.

19 cc of 48 % hydrobromic acid are added dropwise at 0°C over a periodof 15 minutes and while stirring, to 27.7. g of2-cyclopropyl-4-isopropoxy-2-butanol [Method of M. Julia et al., Bull.Soc. Chim. France 1072 (1960)]. The mixture is stirred at 0°-5° for 30minutes and is subsequently extracted with ether. The ether extract iswashed with water, saturated sodium bicarbonate solution, and saturatedsalt solution, dried over sodium sulphate and the ether evaporated off.

The residue is chromatographed with hexane/ethyl acetate (98:2 and 95:5)on silica gel. The chromatographically pure mixture of the cis-transisomers of 1-bromo-6-isopropoxy-4-methyl-3-hexene is obtained ascolourless oil.

n.sub. D²⁰ = 1.4802

Analysis: C₁₀ H₁₉ BrO - Molecular weight: 235.2: Calc. C 51.1 %; H 8.1%; Br 34.0 %; Found C 51.1 %; H 8.3 %; 33.2 %

Compounds of formula XII: The following Examples 25 and 26 arerepresentative of the process for producing the ketones of formula XII,wherein R₂ signifies a lower alkyl group of 1 to 4 carbon atoms.

EXAMPLE 25: 5-Isopropoxy-2-butanone

0.3 g of concentrated sulphuric acid is added to 7.2 g (0.12 mol) ofisopropanol. A mixture of 21 g (0.33 mol) of vinyl methyl ketone and 36g (0.6 mol) of isopropanol is added dropwise at room temperature over aperiod of 1 hour and while stirring, the temperature not exceeding 30°.After 24 hours 1.6 g of potassium carbonate and 2 drops of water areadded at room temperature, the mixture is vigorously stirred for 2hours, is filtered and the clear neutral filtrate is fractionated at 36mm. The excess of isopropanol is first distilled off and then the4-isopropoxy-2-butanone distills over at 73°-76°/36 mm.

EXAMPLE 26: 4-Isopropylthio-2-butanone

The above compound is produced in analogous manner to that described inExample 24, but using isopropyl mercaptan in the place of isopropanol.B.P. 94°-96°/17 mm.

Compounds of formula VIII: The following Examples are representative ofthe process for producing the alcohols of formula VIII.

EXAMPLE 27: 5-Isopropoxy-3-methyl-1-penten-3-ol

12 g (0.5 mol) of magnesium turnings are covered with a layer of 60 ccof absolute tetrahydrofurane in an atmosphere of nitrogen in a flaskequipped with a stirrer and a reflux condenser and heated to 40°-45°. 5cc of a solution of 53.5 g (0.5 mol) of vinyl bromide in 100 cc ofabsolute tetrahydrofurane are added dropwise by means of a droppingfunnel, whereupon an exothermic reaction commences. The remaining vinylbromide solution is added dropwise at such rate that the reactionmixture is maintained at a temperature of 45°-50° (approximately 1 to11/2 hours). The mixture is then stirred at 50° for 1 hour and issubsequently cooled to 0°. 52 g (0.4 mol) of 4-isopropoxy-2-butanone in100 cc of absolute tetrahydrofurane are added dropwise over a period, of45 minutes and while stirring vigorously and the reaction mixture issubsequently stirred at room temperature over a period of 16 hours.After this period 250 cc of 20 % ammonium chloride solution are addedover a period of 15 minutes to the reaction mixture which is cooled to5°-10°. The mixture is stirred for 15 minutes and is extracted withether. The ether extract is washed with water in a separating funnel,dried with sodium sulphate and evaporated. The residue is fractionatedat a pressure of 13 mm, whereby the 5-isopropoxy-3-methyl-penten-3-oldistills over at 72°-73°.

n_(D) ²⁰ = 1.4297

Analysis: C₉ H₁₈ O₂ - Molecular weight: 158.2: Calc. C 68.3 %; H 11.5 %;Found C 68.1 %; H 11.4 %

EXAMPLE 28: 5-Isopropylthio-3-methyl-1-penten-3-ol

The above compound is produced in analogous manner to that described inExample 27, but using 4-isopropylthio-2-butanone in place of4-isopropoxy-2-butanone. B.P. 70°-80°/1.2 mm.

n_(D) ²⁰ = 1.4813

Analysis: C₉ H₁₈ OS - Molecular weight: 174.3: Calc. C 62.0 %; H 10.4 %;S 18.4 %; Found C 61.5 %; H 10.4 %; S 18.9 %

What is claimed is:
 1. A compound of the formula: ##EQU36## wherein R₁is alkyl of 1 to 6 carbon atoms, cyclohexyl, cyclohexyl monosubstitutedby alkyl of 1 to 4 carbon atoms, 4-(cyclohexyl)-n-butyl ringmonosubstituted by n-butyl, 2-cyclo-hexenyl, 3-cyclohexenylmonosubstituted by alkyl of 1 to 4 carbon atoms or4-(3-cyclohexenyl)-n-butyl ring monosubstituted by n-butyl,R₂ ishydrogen or alkyl of 1 to 4 carbon atoms, R₆ is alkyl of 1 to 5 carbonatoms, Z₁ -z₂ is ##EQU37## and n is 2 or
 3. 2. A compound of claim 1 ofthe formula: ##EQU38## wherein R₁ is alkyl of 1 to 6 carbon atoms,cyclohexyl, cyclohexyl monosubstituted by alkyl of 1 to 4 carbon atoms,4-(cyclohexyl)-n-butyl ring monosubstituted by n-butyl, 2-cyclohexenyl,3-cyclohexenyl monosubstituted by alkyl of 1 to 4 carbon atoms or4-(3-cyclohexenyl-n-butyl ring monosubstituted by n-butyl,R₂ is hydrogenor alkyl of 1 to 4 carbon atoms, R₆ is alkyl of 1 to 5 carbon atoms, andZ₁ -z₂ is ##EQU39##
 3. A compound of claim 2 of the formula: ##EQU40##wherein R₁ is isopropyl or sec. butyl, R₂ is hydrogen or methyl,R₆ ismethyl or ethyl, and Z₁ -z₂ is ##EQU41##
 4. The compound of claim 2which is methyl-[9-cyclohexyloxy-3,7-dimethyl]-2,6-nonadienoate.
 5. Thecompound of claim 2, which ismethyl-[9-sec.butoxy-3,7-dimethyl]-2,6-nonadienoate.
 6. The compound ofclaim 2, which is methyl[9-isopropoxy-3,7-dimethyl]-2,6-nonadienoate. 7.The compound of claim 1, which isethyl[10-isopropoxy-3-methyl]-2-decenoate.
 8. The compound of claim 2,which is ethyl[9-isopropoxy-3,7-dimethyl]-2-nonenoate.